PtxCoyCatalysts Degradation in PEFC Environments: Mechanistic Insights: I. Multiscale Modeling

In this article, we focus on the understanding of the PtxCoyelectrocatalysts degradation in polymer electrolyte fuel cell (PEFC) environments. A multiscale atomistic/kinetic model is derived providing mechanistic insights on the impact of the nanostructure and operating conditions on PtxCoynanoparticles durability. On the basis of ab initio (AI) data, we identify favorable pathways of the oxygen reduction reaction (ORR) on PtxCoynanoparticles and of the competitive Pt–Co dissolution in acidic media. The derived AI kinetics is coupled to a description of the atomic reorganization at the nanoparticle level as a function of the cumulated Pt and Co mass losses. This nanoscale model is coupled with a transport microscale model of charges and O2through a PEFC cathode, and simulation sensitivity studies to operating conditions and initial compositions/morphologies are performed and complimented by microstructural and electrochemical characterizations carried out on aging direct liquid injection metallorganic chemical vapor deposition elaborated model electrodes detailed in our experimental companion paper.